Compounds for electronic devices

ABSTRACT

The present invention relates to compounds of the formula (1), to the use thereof in electronic devices, and to electronic devices, particularly organic electroluminescence devices, comprising said compounds according to the invention, particularly as blue emitting material in an emitting layer.

RELATED APPLICATIONS

This application is a divisional application of U.S. patent applicationSer. No. 13/001,818, filed Dec. 29, 2010, which is a national stageapplication (under 35 U.S.C. § 371) of PCT/EP2009/003602, filed May 20,2009, which claims benefit of German Application No. 10 2008 035 413.9,filed Jul. 29, 2008.

The present invention describes novel organic compounds and the usethereof in electronic devices.

The general structure of organic electroluminescent devices isdescribed, for example, in U.S. Pat. No. 4,539,507, U.S. Pat. No.5,151,629, EP 0676461 and WO 98/27136. However, these devices stillexhibit problems for which there is a need for improvement:

-   1. There is still a need for improvement in the efficiency,    especially in the case of fluorescent OLEDs. This applies in    particular to dark-blue-emitting OLEDs.-   2. A further improvement in the operating lifetime is still    desirable, in particular in the case of blue emission.-   3. The operating voltage is quite high, especially in the case of    fluorescent OLEDs. There is therefore still a need for improvement    here in order to improve the power efficiency. This is of major    importance, in particular, for mobile applications.-   4. Many blue-emitting materials in accordance with the prior art are    incompatible with frequently used electron-injection and -transport    materials, such as, for example, hydroxyquinolinate/metal complexes    (for example Alq, Beq), benzimidazole derivatives, phenanthroline    derivatives (for example BCP) or anthracene derivatives, which are    mixed with donors, such as alkali or alkaline-earth metals (for    example Li, Na, K, Rb or Cs), with inorganic salts thereof (for    example LiF or Cs₂CO₃) or with organic salts thereof (for example    lithium, sodium, potassium, rubidium or caesium quinolinate) and    thus produce an excess of electrons in the device. This    incompatibility only results in inadequate device lifetimes. The    problems frequently occur, in particular, if the blue-emitting    material used is a diarylamino derivative of a condensed aromatic    compound. However, emitters of this type are the most frequent and    hitherto the best blue emitters. Further improvements are therefore    desirable here.

The closest prior art for blue-fluorescent emitters aredibenzoindenofluorene derivatives in accordance with WO 07/140847 andmonobenzoindenofluorene derivatives in accordance with WO 08/006449. Inorder to obtain efficient blue emitters from these basic structures, theintroduction of one or two diarylamino groups is necessary. Goodblue-emitting OLEDs have already been achieved with these compounds.However, further improvements are also desirable here with respect tothe efficiency. Whereas these diarylamino-substituted compounds alsoexhibit very good lifetimes in combination with an undopedelectron-transport layer, the lifetime is still inadequate if thesecompounds are used in combination with a doped electron-transport layer,as described above. Further improvements are therefore also necessarywith respect to the lifetime, in particular in combination with dopedelectron-transport layers which result in an excess of electrons in thedevice.

Surprisingly, it has been found that compounds in which three aryl orheteroaryl groups are bridged by two indeno bridges or correspondingheterobridges exhibit particularly good properties as blue emitters if,in particular, the sum of the π electrons of the three aromatic orheteroaromatic groups is a least 28. It is not necessary to introducediarylamino substituents into these compounds since the unsubstitutedcompounds already exhibit highly efficient dark-blue emission.Furthermore, the compounds result in very good lifetimes in organicelectroluminescent devices. The present invention therefore relates tothese compounds and to the use thereof in organic electroluminescentdevices.

The invention therefore relates to compounds of the formula (1)

where the following applies to the symbols and indices used:

-   Ar¹, Ar², Ar³ are on each occurrence, identically or differently, an    aryl or heteroaryl group having 5 to 30 aromatic ring atoms, which    may be substituted by one or more radicals R¹, with the proviso that    Ar² does not stand for anthracene, naphthacene or pentacene;-   X is on each occurrence, identically or differently, a group    selected from BR², C(R²)₂, Si(R²)₂, C═O, C═NR², C═C(R²)₂, O, S, S═O,    SO₂, NR², PR², P(═O)R² and P(═S)R²;-   R¹, R² are on each occurrence, identically or differently, H, D, F,    Cl, Br, I, N(Ar⁴)₂, C(═O)Ar⁴, P(═O)(Ar⁴)₂, S(═O)Ar⁴, S(═O)₂Ar⁴,    CR²═CR²Ar⁴, CHO, CR³═C(R³)₂, CN, NO₂, Si(R³)₃, B(OR³)₂, B(R³)₂,    B(N(R³)₂)₂, OSO₂R³, a straight-chain alkyl, alkoxy or thioalkoxy    group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl    group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl,    alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of    which may be substituted by one or more radicals R³, where in each    case one or more non-adjacent CH₂ groups may be replaced by R³C═CR³,    C≡C, Si(R³)₂, Ge(R³)₂, Sn(R³)₂, C═O, C═S, C═Se, C═NR³, P(═O)R³, SO,    SO₂, NR³, O, S or CONR³ and where one or more H atoms may be    replaced by F, Cl, Br, I, CN or NO₂, or an aromatic or    heteroaromatic ring system having 5 to 60 aromatic ring atoms, which    may in each case be substituted by one or more radicals R³, or a    combination of these systems; two or more substituents R¹ or R² here    may also form a mono- or polycyclic, aliphatic or aromatic ring    system with one another;-   R³ is on each occurrence, identically or differently, H, D or an    aliphatic or aromatic hydrocarbon radical having 1 to 20 C atoms;-   Ar⁴ is on each occurrence, identically or differently, an aromatic    or heteroaromatic ring system having 5-30 aromatic ring atoms, which    may be substituted by one or more non-aromatic radicals R¹; two    radicals Ar on the same nitrogen or phosphorus atom may also be    linked to one another here by a single bond or a bridge X;-   m, n are 0 or 1, with the proviso that m+n=1;-   p is 1, 2, 3, 4, 5 or 6;    Ar¹, Ar² and X here together form a five-membered ring or a    six-membered ring, and Ar², Ar³ and X together form a five-membered    ring or a six-membered ring, with the proviso that either all    symbols X in the compound of the formula (1) are bound in a    five-membered ring or all symbols X in the compound of the    formula (1) are bound in a six-membered ring;    characterised in that the sum of all π electrons in groups Ar¹, Ar²    and Ar³ is at least 28 if p=1 and is at least 34 if p=2 and is at    least 40 if p=3 and is at least 46 if p=4 and is at least 52 if p=5    and is at least 58 if p=6;    the following compounds are excluded from the invention:

n=0 or m=0 here means that the corresponding group X is not present andthat instead hydrogen or a substituent R¹ is bonded to the correspondingpositions of Ar² and Ar³.

The determination of the sum of all π electrons in groups Ar¹, Ar² andAr³ is obvious to the person skilled in the art. Thus, each double bondin an aryl group (where the double bonds are delocalised) stands for twoπ electrons, meaning that, for example, benzene has 6 π electrons,naphthalene has 10 π electrons, anthracene and phenanthrene have 14 πelectrons, pyrene has 16 π electrons, naphthacene, benzanthracene andchrysene have 18 π electrons, and perylene has 20 π electrons. In anaryl group, the number of π electrons corresponds to the number of Catoms in the aromatic ring system. In heteroaromatic compounds, eachdouble bond (the double bonds here are again delocalised) alsocontributes two it electrons, where these delocalised double bonds canbe formed either between two carbon atoms, between carbon and nitrogenor between two nitrogen atoms. Furthermore, in five-membered heteroarylgroups, the heteroatom, which is formally not bonded in a double bond(i.e. for example, the nitrogen in pyrrole, the oxygen in furan or thesulfur in thiophene) likewise contributes two π electrons to the overallπ-electron system via the free electron pair. Pyridine, pyrazine,pyrimidine and pyridazine therefore each have 6 π electrons, quinolineand isoquinoline have 10 π electrons, phenanthroline has 14 π electrons,pyrrole, imidazole, pyrazole, thiophene, thiazole and furan each have 6π electrons, indole, benzimidazole, benzothiophene and benzofuran eachhave 10 π electrons, and carbazole, dibenzothiophene and dibenzofuraneach have 14 π electrons.

It is shown below with reference to the example of phenyl andnaphthalene as groups Ar¹ and Ar² what is meant by the formation of afive-membered ring or six-membered ring from the groups Ar¹, Ar² and X:

With a simple, uncondensed aryl or heteroaryl group, for example withphenyl, it is always only possible to form a five-membered ring. With acondensed aryl or heteroaryl group, for example with naphthalene, theformation of a five-membered ring or six-membered ring is possible,depending on the linking. The same linking principle can be appliedcorrespondingly to other condensed aryl groups or to condensed oruncondensed heteroaryl groups. In a five-membered ring, one edge of thearyl or heteroaryl group Ar¹ or Ar² or Ar³ thus in each case forms afive-membered ring with X. In a six-membered ring, two edges of acondensed aryl or heteroaryl group Ar¹ or Ar² or Ar³ form a six-memberedring together with one edge of a further aryl or heteroaryl group Ar¹ orAr² or Ar³ and together with X.

In a preferred embodiment of the invention, Ar¹, Ar² and X form afive-membered ring and Ar², Ar³ and X form a five-membered ring. If theindex p=2 or 3, two groups Ar² preferably also form a five-membered ringtogether with X.

For the purposes of this invention, an aryl group or heteroaryl group istaken to mean an aromatic group or heteroaromatic group respectivelyhaving a common aromatic electron system, where an aryl group contains 6to 30 C atoms and a heteroaryl group contains 2 to 30 C atoms and atotal of at least 5 aromatic ring atoms. The heteroatoms are preferablyselected from N, O and/or S. For the purposes of this invention, thiscan be a single homo- or heterocyclic ring, for example benzene,pyridine, thiophene, etc., or it can be a condensed aryl or heteroarylgroup in which at least two aromatic or heteroaromatic rings, forexample benzene rings, are fused to one another, i.e. are condensed ontoone another by anellation, i.e. have at least one common edge and thusalso a common aromatic system. This aryl or heteroaryl group may besubstituted or unsubstituted; any substituents present may likewise formfurther ring systems. Thus, for example, systems such as naphthalene,anthracene, phenanthrene, pyrene, etc., are to be regarded as arylgroups for the purposes of this invention and quinoline, acridine,benzothiophene, carbazole, etc., are to be regarded as heteroaryl groupsfor the purposes of this invention, while, for example, biphenyl,fluorene, spirobifluorene, etc., are not aryl groups since separatearomatic electron systems are present here.

For the purposes of this invention, an aromatic ring system contains 6to 60 C atoms in the ring system. For the purposes of this invention, aheteroaromatic ring system contains 2 to 60 C atoms and at least oneheteroatom in the ring system, with the proviso that the total number ofC atoms and heteroatoms is at least 5. The heteroatoms are preferablyselected from N, O and/or S. For the purposes of this invention, anaromatic or heteroaromatic ring system is intended to be taken to mean asystem which does not necessarily contain only aryl or heteroarylgroups, but in which, in addition, a plurality of aryl or heteroarylgroups may be interrupted by a short, non-aromatic unit (less than 10%of the atoms other than H, preferably less than 5% of the atoms otherthan H), such as, for example, a C, N or O atom. Thus, for example,systems such as 9,9′-spirobifluorene, 9,9-diarylfluorene, triarylamine,diaryl ether, etc., are also to be regarded as aromatic ring systems forthe purposes of this invention.

For the purposes of the present invention, a C₁- to C₄₀-alkyl group, inwhich individual H atoms or CH₂ groups may also be substituted by theabove-mentioned groups, is particularly preferably taken to mean theradicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl,t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, tert-pentyl, 2-pentyl,cyclopentyl, n-hexyl, s-hexyl, tert-hexyl, 2-hexyl, 3-hexyl, cyclohexyl,2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl,1-methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl,1-bicyclo[2.2.2]octyl, 2-bicyclo[2.2.2]octyl, 2-(2,6-dimethyl)octyl,3-(3,7-dimethyl)octyl, trifluoromethyl, pentafluoroethyl,2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl,cyclopentenyl, hexenyl, heptynyl, cyclohexenyl, heptenyl, cycloheptenyl,octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl oroctynyl. A C₁- to C₄₀-alkoxy group is particularly preferably taken tomean methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy,s-butoxy, t-butoxy or 2-methylbutoxy. A C₂-C₂₄-aryl or -heteroarylgroup, which can be monovalent or divalent depending on the use, may ineach case also be substituted by the above-mentioned radicals R¹ and maybe linked to the aromatic or heteroaromatic ring system via any desiredpositions, is taken to mean, in particular, groups derived from benzene,naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene,perylene, fluoranthene, benzanthracene, benzophenanthrene,benzofluoranthene, tetracene, pentacene, benzopyrene, furan, benzofuran,isobenzofuran, dibenzofuran, thiophene, benzothiophene,isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole,carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine,benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline,phenothiazine, phenoxazine, pyrazole, indazole, imidazole,benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole,pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole,naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole,1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine,benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine,azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole,1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole,1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole,1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine,1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine,1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine,benzothiadiazole. In addition to the above-mentioned aryl and heteroarylgroups, aromatic and heteroaromatic ring systems are, for the purposesof this invention, taken to mean, in particular, biphenylene,terphenylene, fluorene, benzofluorene, dibenzofluorene, spirobifluorene,dihydrophenanthrene, tetrahydropyrene, cis- or trans-indenofluorene,cis- or trans-monobenzoindenofluorene or cis- ortrans-dibenzoindenofluorene.

In a preferred embodiment of the invention, the index p=1, 2 or 3,particularly preferably 1 or 2, very particularly preferably 1.

In a preferred embodiment of the invention, the sum of all π electronsin groups Ar¹, Ar² and Ar³ is between 28 and 50, particularly preferablybetween 28 and 46, very particularly preferably between 28 and 42, inparticular between 28 and 36, if p=1, and is between 34 and 56,particularly preferably between 34 and 52, very particularly preferablybetween 34 and 48, in particular between 34 and 40, if p=2, and isbetween 40 and 62, particularly preferably between 40 and 58, veryparticularly preferably between 40 and 54, in particular between 40 and46, if p=3.

Preference is furthermore given to compounds of the formula (1) in whichthe symbols Ar¹, Ar² and Ar³ stand, identically or differently on eachoccurrence, for an aryl or heteroaryl group having 5 to 22 aromatic ringatoms, in particular having 5 to 18 aromatic ring atoms. The groups Ar¹,Ar² and Ar³ here are particularly preferably selected, independently ofone another, from the group consisting of benzene, naphthalene,anthracene, phenanthrene, fluoranthene, naphthacene, benzanthracene,chrysene, pyrene, benzofluoranthene, triphenylene, perylene,dibenzanthracene, benzopyrene, picene, pentacene, pentaphene,benzophenanthrene, pyridine, pyrazine, pyrimidine, pyridazine,quinoline, isoquinoline, phenanthroline, acridine. The symbols Ar¹, Ar²and Ar³ particularly preferably stand on each occurrence, identically ordifferently, for an aryl group having 6 to 18 aromatic ring atoms, inparticular selected from benzene, naphthalene, anthracene, phenanthrene,fluoranthene, naphthacene, benzanthracene, chrysene, pyrene,benzofluoranthene and triphenylene.

Particularly preferred groups Ar¹ and Ar³ which form a five-memberedring with Ar² are the groups of the formulae (2) to (85) shown below,each of which may be substituted by one or more radicals R¹. Thesymbol * stands for the position of the link from Ar¹ or Ar³ to Ar², andthe symbol # stands for the position of the link from Ar¹ or Ar³ to X.

Preference is likewise given to the groups Ar¹ and Ar³ mentioned abovewhich form a six-membered ring with Ar². The formation of a six-memberedring takes place via two groups in the peri position, as depicted by wayof example below with reference to the example of an anthracene group:

Particularly preferred groups Ar² are the groups of the formulae (86) to(110) shown below, each of which may be substituted by one or moreradicals R¹. The symbol * stands for the position of the link from Ar²to Ar¹ or Ar³ and the symbol # stands for the position of the link fromAr² to X.

Entirely analogously, groups Ar² which form a six-membered ring with Ar¹or Ar³ and X are also possible here.

Preference is furthermore given to compounds in which at least one ofthe groups Ar¹, Ar² and Ar³ has at least three condensed rings, i.e. atleast 14 π electrons. Particularly preferably, at least one of thegroups Ar¹, Ar² and Ar³ has at least 4 condensed rings, i.e. at least 16π electrons. Very particularly preferably, at least one of the groupsAr¹, Ar² and Ar³ has at least 4 condensed rings, i.e. at least 16 πelectrons, and at least one of the other two groups Ar¹, Ar² or Ar³ hasat least 2 condensed rings, i.e. at least 10 π electrons.

Preferred combinations of Ar¹, Ar² and Ar³ are the combinations shown inTable 1 and Table 2. Ar¹, Ar² and Ar³ here may also be substituted byone or more radicals R¹.

TABLE 1 Ar1 Ar2 Ar3 Benzene Benzene Pyrene Benzene Benzene NaphthaceneBenzene Benzene Benzathracene Benzene Benzene Chrysene Benzene BenzeneBenzophenanthrene Benzene Benzene Fluoranthene Benzene BenzeneTriphenylene Benzene Naphthalene Anthracene Benzene NaphthalenePhenanthrene Benzene Naphthalene Pyrene Benzene Naphthalene NaphthaceneBenzene Naphthalene Benzathracene Benzene Naphthalene Chrysene BenzeneNaphthalene Benzophenanthrene Benzene Naphthalene Fluoranthene BenzeneNaphthalene Triphenylene Naphthalene Benzene Anthracene NaphthaleneBenzene Phenanthrene Naphthalene Benzene Pyrene Naphthalene BenzeneNaphthacene Naphthalene Benzene Benzathracene Naphthalene BenzeneChrysene Naphthalene Benzene Benzophenanthrene Naphthalene BenzeneFluoranthene Naphthalene Benzene Triphenylene Naphthalene NaphthaleneNaphthalene Naphthalene Naphthalene Anthracene Naphthalene NaphthalenePhenanthrene Naphthalene Naphthalene Pyrene Naphthalene NaphthaleneNaphthacene Naphthalene Naphthalene Benzathracene NaphthaleneNaphthalene Chrysene Naphthalene Naphthalene BenzophenanthreneNaphthalene Naphthalene Fluoranthene Naphthalene NaphthaleneTriphenylene Anthracene Benzene Anthracene Anthracene BenzenePhenanthrene Anthracene Benzene Pyrene Anthracene Benzene NaphthaceneAnthracene Benzene Benzathracene Anthracene Benzene Chrysene AnthraceneBenzene Benzophenanthrene Anthracene Benzene Fluoranthene AnthraceneBenzene Triphenylene Anthracene Naphthalene Anthracene AnthraceneNaphthalene Phenanthrene Anthracene Naphthalene Pyrene AnthraceneNaphthalene Naphthacene Anthracene Naphthalene Benzathracene AnthraceneNaphthalene Chrysene Anthracene Naphthalene Benzophenanthrene AnthraceneNaphthalene Fluoranthene Anthracene Naphthalene TriphenylenePhenanthrene Benzene Phenanthrene Phenanthrene Benzene PyrenePhenanthrene Benzene Naphthacene Phenanthrene Benzene BenzathracenePhenanthrene Benzene Chrysene Phenanthrene Benzene BenzophenanthrenePhenanthrene Benzene Fluoranthene Phenanthrene Benzene TriphenylenePhenanthrene Naphthalene Phenanthrene Phenanthrene Naphthalene PyrenePhenanthrene Naphthalene Naphthacene Phenanthrene NaphthaleneBenzathracene Phenanthrene Naphthalene Chrysene Phenanthrene NaphthaleneBenzophenanthrene Phenanthrene Naphthalene Fluoranthene PhenanthreneNaphthalene Triphenylene Pyrene Benzene Pyrene Pyrene BenzeneNaphthacene Pyrene Benzene Benzathracene Pyrene Benzene Chrysene PyreneBenzene Benzophenanthrene Pyrene Benzene Fluoranthene Pyrene BenzeneTriphenylene Pyrene Naphthalene Pyrene Pyrene Naphthalene NaphthacenePyrene Naphthalene Benzathracene Pyrene Naphthalene Chrysene PyreneNaphthalene Benzophenanthrene Pyrene Naphthalene Fluoranthene PyreneNaphthalene Triphenylene Naphthacene Benzene Naphthacene NaphthaceneBenzene Benzathracene Naphthacene Benzene Chrysene Naphthacene BenzeneBenzophenanthrene Naphthacene Benzene Fluoranthene Naphthacene BenzeneTriphenylene Naphthacene Naphthalene Naphthacene Naphthacene NaphthaleneBenzathracene Naphthacene Naphthalene Chrysene Naphthacene NaphthaleneBenzophenanthrene Naphthacene Naphthalene Fluoranthene NaphthaceneNaphthalene Triphenylene Benzathracene Benzene BenzathraceneBenzathracene Benzene Chrysene Benzathracene Benzene BenzophenanthreneBenzathracene Benzene Fluoranthene Benzathracene Benzene TriphenyleneBenzathracene Naphthalene Benzathracene Benzathracene NaphthaleneChrysene Benzathracene Naphthalene Benzophenanthrene BenzathraceneNaphthalene Fluoranthene Benzathracene Naphthalene Triphenylene ChryseneBenzene Chrysene Chrysene Benzene Benzophenanthrene Chrysene BenzeneFluoranthene Chrysene Benzene Triphenylene Chrysene Naphthalene ChryseneChrysene Naphthalene Benzophenanthrene Chrysene Naphthalene FluorantheneChrysene Naphthalene Triphenylene Benzophenanthrene BenzeneBenzophenanthrene Benzophenanthrene Benzene FluorantheneBenzophenanthrene Benzene Triphenylene Benzophenanthrene NaphthaleneBenzophenanthrene Benzophenanthrene Naphthalene FluorantheneBenzophenanthrene Naphthalene Triphenylene Fluoranthene BenzeneFluoranthene Fluoranthene Benzene Triphenylene Fluoranthene NaphthaleneFluoranthene Fluoranthene Naphthalene Triphenylene Triphenylene BenzeneTriphenylene Triphenylene Naphthalene Triphenylene

The above-mentioned units are preferably selected from the units of theformulae (2) to (110). Thus, for Ar¹ or Ar³ in Table 1, the benzene isselected from the formula (2), the naphthalene is selected fromstructures of the formulae (3) to (5), the pyrene is selected fromstructures of the formulae (16) to (18), the naphthacene is selectedfrom structures of the formulae (33) to (35), the benzanthracene isselected from structures of the formulae (36) to (49), the chrysene isselected from structures of the formulae (50) to (57), thebenzophenanthrene is selected from structures of the formulae (58) to(65), the fluoranthene is selected from structures of the formulae (19)to (32) and the triphenylene is selected from structures of the formulae(66) to (68). For the group Ar², the benzene is selected from structuresof the formulae (96) to (100) and the naphthalene is selected fromstructures of the formulae (101) to (105). These structures may each besubstituted by one or more radicals R¹.

TABLE 2 Ar1 Ar2 Ar3 Benzene Phenanthrene Naphthalene BenzenePhenanthrene Anthracene Benzene Phenanthrene Phenanthrene BenzenePhenanthrene Pyrene Benzene Phenanthrene Naphthacene BenzenePhenanthrene Benzanthracene Benzene Phenanthrene Chrysene BenzenePhenanthrene Benzophenanthrene Benzene Phenanthrene Fluoranthene BenzenePhenanthrene Triphenylene Benzene Pyrene Benzene Benzene PyreneNaphthalene Benzene Pyrene Anthracene Benzene Pyrene PhenanthreneBenzene Pyrene Pyrene Benzene Pyrene Naphthacene Benzene PyreneBenzanthracene Benzene Pyrene Chrysene Benzene Pyrene BenzophenanthreneBenzene Pyrene Fluoranthene Benzene Pyrene Triphenylene BenzeneBenzanthracene Benzene Benzene Benzanthracene Naphthalene BenzeneBenzanthracene Anthracene Benzene Benzanthracene Phenanthrene BenzeneBenzanthracene Pyrene Benzene Benzanthracene Naphthacene BenzeneBenzanthracene Benzanthracene Benzene Benzanthracene Chrysene BenzeneBenzanthracene Benzophenanthrene Benzene Benzanthracene FluorantheneBenzene Benzanthracene Triphenylene Benzene Chrysene Benzene BenzeneChrysene Naphthalene Benzene Chrysene Anthracene Benzene ChrysenePhenanthrene Benzene Chrysene Pyrene Benzene Chrysene NaphthaceneBenzene Chrysene Benzanthracene Benzene Chrysene Chrysene BenzeneChrysene Benzophenanthrene Benzene Chrysene Fluoranthene BenzeneChrysene Triphenylene Benzene Benzophenanthrene Benzene BenzeneBenzophenanthrene Naphthalene Benzene Benzophenanthrene AnthraceneBenzene Benzophenanthrene Phenanthrene Benzene Benzophenanthrene PyreneBenzene Benzophenanthrene Naphthacene Benzene BenzophenanthreneBenzanthracene Benzene Benzophenanthrene Chrysene BenzeneBenzophenanthrene Benzophenanthrene Benzene BenzophenanthreneFluoranthene Benzene Benzophenanthrene Triphenylene Benzene FluorantheneBenzene Benzene Fluoranthene Naphthalene Benzene Fluoranthene AnthraceneBenzene Fluoranthene Phenanthrene Benzene Fluoranthene Pyrene BenzeneFluoranthene Naphthacene Benzene Fluoranthene Benzanthracene BenzeneFluoranthene Chrysene Benzene Fluoranthene Benzophenanthrene BenzeneFluoranthene Fluoranthene Benzene Fluoranthene Triphenylene BenzeneTriphenylene Benzene Benzene Triphenylene Naphthalene BenzeneTriphenylene Anthracene Benzene Triphenylene Phenanthrene BenzeneTriphenylene Pyrene Benzene Triphenylene Naphthacene BenzeneTriphenylene Benzanthracene Benzene Triphenylene Chrysene BenzeneTriphenylene Benzophenanthrene Benzene Triphenylene Fluoranthene BenzeneTriphenylene Triphenylene Naphthalene Phenanthrene Benzene NaphthalenePhenanthrene Naphthalene Naphthalene Phenanthrene Anthracene NaphthalenePhenanthrene Phenanthrene Naphthalene Phenanthrene Pyrene NaphthalenePhenanthrene Naphthacene Naphthalene Phenanthrene BenzanthraceneNaphthalene Phenanthrene Chrysene Naphthalene PhenanthreneBenzophenanthrene Naphthalene Phenanthrene Fluoranthene NaphthalenePhenanthrene Triphenylene Naphthalene Pyrene Benzene Naphthalene PyreneNaphthalene Naphthalene Pyrene Anthracene Naphthalene PyrenePhenanthrene Naphthalene Pyrene Pyrene Naphthalene Pyrene NaphthaceneNaphthalene Pyrene Benzanthracene Naphthalene Pyrene ChryseneNaphthalene Pyrene Benzophenanthrene Naphthalene Pyrene FluorantheneNaphthalene Pyrene Triphenylene Naphthalene Benzanthracene BenzeneNaphthalene Benzanthracene Naphthalene Naphthalene BenzanthraceneAnthracene Naphthalene Benzanthracene Phenanthrene NaphthaleneBenzanthracene Pyrene Naphthalene Benzanthracene Naphthacene NaphthaleneBenzanthracene Benzanthracene Naphthalene Benzanthracene ChryseneNaphthalene Benzanthracene Benzophenanthrene Naphthalene BenzanthraceneFluoranthene Naphthalene Benzanthracene Triphenylene NaphthaleneChrysene Benzene Naphthalene Chrysene Naphthalene Naphthalene ChryseneAnthracene Naphthalene Chrysene Phenanthrene Naphthalene Chrysene PyreneNaphthalene Chrysene Naphthacene Naphthalene Chrysene BenzanthraceneNaphthalene Chrysene Chrysene Naphthalene Chrysene BenzophenanthreneNaphthalene Chrysene Fluoranthene Naphthalene Chrysene TriphenyleneNaphthalene Benzophenanthrene Benzene Naphthalene BenzophenanthreneNaphthalene Naphthalene Benzophenanthrene Anthracene NaphthaleneBenzophenanthrene Phenanthrene Naphthalene Benzophenanthrene PyreneNaphthalene Benzophenanthrene Naphthacene Naphthalene BenzophenanthreneBenzanthracene Naphthalene Benzophenanthrene Chrysene NaphthaleneBenzophenanthrene Benzophenanthrene Naphthalene BenzophenanthreneFluoranthene Naphthalene Benzophenanthrene Triphenylene NaphthaleneFluoranthene Benzene Naphthalene Fluoranthene Naphthalene NaphthaleneFluoranthene Anthracene Naphthalene Fluoranthene PhenanthreneNaphthalene Fluoranthene Pyrene Naphthalene Fluoranthene NaphthaceneNaphthalene Fluoranthene Benzanthracene Naphthalene FluorantheneChrysene Naphthalene Fluoranthene Benzophenanthrene NaphthaleneFluoranthene Fluoranthene Naphthalene Fluoranthene TriphenyleneNaphthalene Triphenylene Benzene Naphthalene Triphenylene NaphthaleneNaphthalene Triphenylene Anthracene Naphthalene TriphenylenePhenanthrene Naphthalene Triphenylene Pyrene Naphthalene TriphenyleneNaphthacene Naphthalene Triphenylene Benzanthracene NaphthaleneTriphenylene Chrysene Naphthalene Triphenylene BenzophenanthreneNaphthalene Triphenylene Fluoranthene Naphthalene TriphenyleneTriphenylene

For Ar¹ and Ar³ in Table 2, the benzene is a group of the formula (2),and the naphthalene is selected from structures of the formulae (3) to(5). For the group Ar², the pyrene is selected from structures of theformulae (112) to (115), the naphthacene is selected from structures ofthe formulae (117) to (120), and the triphenylene is selected fromstructures of the formula (116). These structures may each besubstituted by one or more radicals R¹.

Specific particularly preferred combinations of Ar¹, Ar² and Ar³ arerevealed, for example, by Table 3 below. The bridges X for thesestructures are particularly preferably C(R²)₂ groups. Very particularlypreferably, both bridges X stand for C(CH₃)₂ or both bridges X stand forC(phenyl)₂ or one bridge X stands for C(CH₃)₂ and the other bridge Xstands for C(phenyl)₂. The groups Ar¹, Ar² and Ar³ here may besubstituted by one or more radicals R¹, but are preferablyunsubstituted.

TABLE 3 No. Ar1 Ar2 Ar3 1 Formula (2) Formula (86) Formula (17) 2Formula (2) Formula (86) Formula (28) 3 Formula (2) Formula (86) Formula(41) 4 Formula (2) Formula (87) Formula (17) 5 Formula (2) Formula (87)Formula (28) 6 Formula (2) Formula (87) Formula (41) 7 Formula (2)Formula (91) Formula (7) 8 Formula (2) Formula (91) Formula (8) 9Formula (2) Formula (91) Formula (13) 10 Formula (2) Formula (91)Formula (17) 11 Formula (2) Formula (91) Formula (28) 12 Formula (2)Formula (91) Formula (41) 13 Formula (2) Formula (93) Formula (7) 14Formula (2) Formula (93) Formula (8) 15 Formula (2) Formula (93) Formula(13) 16 Formula (2) Formula (93) Formula (17) 17 Formula (2) Formula(93) Formula (28) 18 Formula (2) Formula (93) Formula (41) 19 Formula(2) Formula (95) Formula (7) 20 Formula (2) Formula (95) Formula (8) 21Formula (2) Formula (95) Formula (13) 22 Formula (2) Formula (95)Formula (17) 23 Formula (2) Formula (95) Formula (28) 24 Formula (2)Formula (95) Formula (41) 25 Formula (2) Formula (102) Formula (2) 26Formula (2) Formula (102) Formula (3) 27 Formula (2) Formula (102)Formula (4) 28 Formula (2) Formula (102) Formula (7) 29 Formula (2)Formula (102) Formula (8) 30 Formula (2) Formula (102) Formula (13) 31Formula (2) Formula (102) Formula (17) 32 Formula (2) Formula (102)Formula (28) 33 Formula (2) Formula (102) Formula (41) 34 Formula (3)Formula (86) Formula (7) 35 Formula (3) Formula (86) Formula (8) 36Formula (3) Formula (86) Formula (13) 37 Formula (3) Formula (86)Formula (17) 38 Formula (3) Formula (86) Formula (28) 39 Formula (3)Formula (86) Formula (41) 40 Formula (3) Formula (87) Formula (7) 41Formula (3) Formula (87) Formula (8) 42 Formula (3) Formula (87) Formula(13) 43 Formula (3) Formula (87) Formula (17) 44 Formula (3) Formula(87) Formula (28) 45 Formula (3) Formula (87) Formula (41) 46 Formula(3) Formula (91) Formula (3) 47 Formula (3) Formula (91) Formula (4) 48Formula (3) Formula (91) Formula (7) 49 Formula (3) Formula (91) Formula(8) 50 Formula (3) Formula (91) Formula (13) 51 Formula (3) Formula (91)Formula (17) 52 Formula (3) Formula (91) Formula (28) 52 Formula (3)Formula (91) Formula (41) 53 Formula (3) Formula (93) Formula (3) 54Formula (3) Formula (93) Formula (4) 55 Formula (3) Formula (93) Formula(7) 56 Formula (3) Formula (93) Formula (8) 57 Formula (3) Formula (93)Formula (13) 58 Formula (3) Formula (93) Formula (17) 59 Formula (3)Formula (93) Formula (28) 60 Formula (3) Formula (93) Formula (41) 61Formula (3) Formula (95) Formula (3) 62 Formula (3) Formula (95) Formula(4) 63 Formula (3) Formula (95) Formula (7) 64 Formula (3) Formula (95)Formula (8) 65 Formula (3) Formula (95) Formula (13) 66 Formula (3)Formula (95) Formula (17) 67 Formula (3) Formula (95) Formula (28) 68Formula (3) Formula (95) Formula (41) 69 Formula (3) Formula (102)Formula (2) 70 Formula (3) Formula (102) Formula (3) 71 Formula (3)Formula (102) Formula (4) 72 Formula (3) Formula (102) Formula (7) 73Formula (3) Formula (102) Formula (8) 74 Formula (3) Formula (102)Formula (13) 75 Formula (3) Formula (102) Formula (17) 76 Formula (3)Formula (102) Formula (28) 77 Formula (3) Formula (102) Formula (41) 78Formula (4) Formula (86) Formula (7) 79 Formula (4) Formula (86) Formula(8) 80 Formula (4) Formula (86) Formula (13) 81 Formula (4) Formula (86)Formula (17) 82 Formula (4) Formula (86) Formula (28) 83 Formula (4)Formula (86) Formula (41) 84 Formula (4) Formula (87) Formula (7) 85Formula (4) Formula (87) Formula (8) 86 Formula (4) Formula (87) Formula(13) 87 Formula (4) Formula (87) Formula (17) 88 Formula (4) Formula(87) Formula (28) 89 Formula (4) Formula (87) Formula (41) 90 Formula(4) Formula (91) Formula (3) 91 Formula (4) Formula (91) Formula (4) 92Formula (4) Formula (91) Formula (7) 93 Formula (4) Formula (91) Formula(8) 94 Formula (4) Formula (91) Formula (13) 95 Formula (4) Formula (91)Formula (17) 96 Formula (4) Formula (91) Formula (28) 97 Formula (4)Formula (91) Formula (41) 98 Formula (4) Formula (93) Formula (2) 99Formula (4) Formula (93) Formula (3) 100 Formula (4) Formula (93)Formula (4) 101 Formula (4) Formula (93) Formula (7) 102 Formula (4)Formula (93) Formula (8) 103 Formula (4) Formula (93) Formula (13) 104Formula (4) Formula (93) Formula (17) 105 Formula (4) Formula (93)Formula (28) 106 Formula (4) Formula (93) Formula (41) 107 Formula (4)Formula (95) Formula (2) 108 Formula (4) Formula (95) Formula (3) 109Formula (4) Formula (95) Formula (4) 110 Formula (4) Formula (95)Formula (7) 111 Formula (4) Formula (95) Formula (8) 112 Formula (4)Formula (95) Formula (13) 113 Formula (4) Formula (95) Formula (17) 114Formula (4) Formula (95) Formula (28) 115 Formula (4) Formula (95)Formula (41) 116 Formula (4) Formula (102) Formula (2) 117 Formula (4)Formula (102) Formula (3) 118 Formula (4) Formula (102) Formula (4) 119Formula (4) Formula (102) Formula (7) 120 Formula (4) Formula (102)Formula (8) 121 Formula (4) Formula (102) Formula (13) 122 Formula (4)Formula (102) Formula (17) 123 Formula (4) Formula (102) Formula (28)124 Formula (4) Formula (102) Formula (41) 125 Formula (7) Formula (86)Formula (3) 126 Formula (7) Formula (86) Formula (4) 127 Formula (7)Formula (86) Formula (7) 128 Formula (7) Formula (86) Formula (8) 129Formula (7) Formula (86) Formula (13) 130 Formula (7) Formula (86)Formula (17) 131 Formula (7) Formula (86) Formula (28) 132 Formula (7)Formula (86) Formula (41) 133 Formula (7) Formula (87) Formula (3) 134Formula (7) Formula (87) Formula (4) 135 Formula (7) Formula (87)Formula (7) 136 Formula (7) Formula (87) Formula (8) 137 Formula (7)Formula (87) Formula (13) 138 Formula (7) Formula (87) Formula (17) 139Formula (7) Formula (87) Formula (28) 140 Formula (7) Formula (87)Formula (41) 141 Formula (7) Formula (91) Formula (2) 142 Formula (7)Formula (91) Formula (3) 143 Formula (7) Formula (91) Formula (4) 144Formula (7) Formula (91) Formula (7) 145 Formula (7) Formula (91)Formula (8) 146 Formula (7) Formula (91) Formula (13) 147 Formula (7)Formula (91) Formula (17) 148 Formula (7) Formula (91) Formula (28) 149Formula (7) Formula (91) Formula (41) 150 Formula (7) Formula (93)Formula (2) 151 Formula (7) Formula (93) Formula (3) 152 Formula (7)Formula (93) Formula (4) 153 Formula (7) Formula (93) Formula (7) 154Formula (7) Formula (93) Formula (8) 155 Formula (7) Formula (93)Formula (13) 156 Formula (7) Formula (93) Formula (17) 157 Formula (7)Formula (93) Formula (28) 158 Formula (7) Formula (93) Formula (41) 159Formula (7) Formula (95) Formula (2) 160 Formula (7) Formula (95)Formula (3) 161 Formula (7) Formula (95) Formula (4) 162 Formula (7)Formula (95) Formula (7) 163 Formula (7) Formula (95) Formula (8) 164Formula (7) Formula (95) Formula (13) 165 Formula (7) Formula (95)Formula (17) 166 Formula (7) Formula (95) Formula (28) 167 Formula (7)Formula (95) Formula (41) 168 Formula (7) Formula (102) Formula (2) 169Formula (7) Formula (102) Formula (3) 170 Formula (7) Formula (102)Formula (4) 171 Formula (7) Formula (102) Formula (7) 172 Formula (7)Formula (102) Formula (8) 173 Formula (7) Formula (102) Formula (13) 174Formula (7) Formula (102) Formula (17) 175 Formula (7) Formula (102)Formula (28) 176 Formula (7) Formula (102) Formula (41) 177 Formula (8)Formula (86) Formula (3) 178 Formula (8) Formula (86) Formula (4) 179Formula (8) Formula (86) Formula (7) 180 Formula (8) Formula (86)Formula (8) 181 Formula (8) Formula (86) Formula (13) 182 Formula (8)Formula (86) Formula (17) 183 Formula (8) Formula (86) Formula (28) 184Formula (8) Formula (86) Formula (41) 185 Formula (8) Formula (87)Formula (3) 186 Formula (8) Formula (87) Formula (4) 187 Formula (8)Formula (87) Formula (7) 188 Formula (8) Formula (87) Formula (8) 189Formula (8) Formula (87) Formula (13) 190 Formula (8) Formula (87)Formula (17) 191 Formula (8) Formula (87) Formula (28) 192 Formula (8)Formula (87) Formula (41) 193 Formula (8) Formula (91) Formula (2) 194Formula (8) Formula (91) Formula (3) 195 Formula (8) Formula (91)Formula (4) 196 Formula (8) Formula (91) Formula (7) 197 Formula (8)Formula (91) Formula (8) 198 Formula (8) Formula (91) Formula (13) 199Formula (8) Formula (91) Formula (17) 200 Formula (8) Formula (91)Formula (28) 201 Formula (8) Formula (91) Formula (41) 202 Formula (8)Formula (93) Formula (2) 203 Formula (8) Formula (93) Formula (3) 204Formula (8) Formula (93) Formula (4) 205 Formula (8) Formula (93)Formula (7) 206 Formula (8) Formula (93) Formula (8) 207 Formula (8)Formula (93) Formula (13) 208 Formula (8) Formula (93) Formula (17) 209Formula (8) Formula (93) Formula (28) 210 Formula (8) Formula (93)Formula (41) 211 Formula (8) Formula (95) Formula (2) 212 Formula (8)Formula (95) Formula (3) 213 Formula (8) Formula (95) Formula (4) 214Formula (8) Formula (95) Formula (7) 215 Formula (8) Formula (95)Formula (8) 216 Formula (8) Formula (95) Formula (13) 217 Formula (8)Formula (95) Formula (17) 218 Formula (8) Formula (95) Formula (28) 219Formula (8) Formula (95) Formula (41) 220 Formula (8) Formula (102)Formula (2) 221 Formula (8) Formula (102) Formula (3) 222 Formula (8)Formula (102) Formula (4) 223 Formula (8) Formula (102) Formula (7) 224Formula (8) Formula (102) Formula (8) 225 Formula (8) Formula (102)Formula (13) 226 Formula (8) Formula (102) Formula (17) 227 Formula (8)Formula (102) Formula (28) 228 Formula (8) Formula (102) Formula (41)229 Formula (13) Formula (86) Formula (3) 230 Formula (13) Formula (86)Formula (4) 231 Formula (13) Formula (86) Formula (7) 232 Formula (13)Formula (86) Formula (8) 233 Formula (13) Formula (86) Formula (13) 234Formula (13) Formula (86) Formula (17) 235 Formula (13) Formula (86)Formula (28) 236 Formula (13) Formula (86) Formula (41) 237 Formula (13)Formula (87) Formula (3) 238 Formula (13) Formula (87) Formula (4) 239Formula (13) Formula (87) Formula (7) 240 Formula (13) Formula (87)Formula (8) 241 Formula (13) Formula (87) Formula (13) 242 Formula (13)Formula (87) Formula (17) 243 Formula (13) Formula (87) Formula (28) 244Formula (13) Formula (87) Formula (41) 245 Formula (13) Formula (91)Formula (2) 246 Formula (13) Formula (91) Formula (3) 247 Formula (13)Formula (91) Formula (4) 248 Formula (13) Formula (91) Formula (7) 249Formula (13) Formula (91) Formula (8) 250 Formula (13) Formula (91)Formula (13) 251 Formula (13) Formula (91) Formula (17) 252 Formula (13)Formula (91) Formula (28) 253 Formula (13) Formula (91) Formula (41) 254Formula (13) Formula (93) Formula (2) 255 Formula (13) Formula (93)Formula (3) 256 Formula (13) Formula (93) Formula (4) 257 Formula (13)Formula (93) Formula (7) 258 Formula (13) Formula (93) Formula (8) 259Formula (13) Formula (93) Formula (13) 260 Formula (13) Formula (93)Formula (17) 261 Formula (13) Formula (93) Formula (28) 262 Formula (13)Formula (93) Formula (41) 263 Formula (13) Formula (95) Formula (2) 264Formula (13) Formula (95) Formula (3) 265 Formula (13) Formula (95)Formula (4) 266 Formula (13) Formula (95) Formula (7) 267 Formula (13)Formula (95) Formula (8) 268 Formula (13) Formula (95) Formula (13) 269Formula (13) Formula (95) Formula (17) 270 Formula (13) Formula (95)Formula (28) 271 Formula (13) Formula (95) Formula (41) 272 Formula (13)Formula (102) Formula (2) 273 Formula (13) Formula (102) Formula (3) 274Formula (13) Formula (102) Formula (4) 275 Formula (13) Formula (102)Formula (7) 276 Formula (13) Formula (102) Formula (8) 277 Formula (13)Formula (102) Formula (13) 278 Formula (13) Formula (102) Formula (17)279 Formula (13) Formula (102) Formula (28) 280 Formula (13) Formula(102) Formula (41) 281 Formula (17) Formula (86) Formula (2) 282 Formula(17) Formula (86) Formula (3) 283 Formula (17) Formula (86) Formula (4)284 Formula (17) Formula (86) Formula (7) 285 Formula (17) Formula (86)Formula (8) 286 Formula (17) Formula (86) Formula (13) 287 Formula (17)Formula (86) Formula (17) 288 Formula (17) Formula (86) Formula (28) 289Formula (17) Formula (86) Formula (41) 290 Formula (17) Formula (87)Formula (2) 291 Formula (17) Formula (87) Formula (3) 292 Formula (17)Formula (87) Formula (4) 293 Formula (17) Formula (87) Formula (7) 294Formula (17) Formula (87) Formula (8) 295 Formula (17) Formula (87)Formula (13) 296 Formula (17) Formula (87) Formula (17) 297 Formula (17)Formula (87) Formula (28) 298 Formula (17) Formula (87) Formula (41) 299Formula (17) Formula (91) Formula (2) 300 Formula (17) Formula (91)Formula (3) 301 Formula (17) Formula (91) Formula (4) 302 Formula (17)Formula (91) Formula (7) 303 Formula (17) Formula (91) Formula (8) 304Formula (17) Formula (91) Formula (13) 305 Formula (17) Formula (91)Formula (17) 306 Formula (17) Formula (91) Formula (28) 307 Formula (17)Formula (91) Formula (41) 308 Formula (17) Formula (93) Formula (2) 309Formula (17) Formula (93) Formula (3) 310 Formula (17) Formula (93)Formula (4) 311 Formula (17) Formula (93) Formula (7) 312 Formula (17)Formula (93) Formula (8) 313 Formula (17) Formula (93) Formula (13) 314Formula (17) Formula (93) Formula (17) 315 Formula (17) Formula (93)Formula (28) 316 Formula (17) Formula (93) Formula (41) 317 Formula (17)Formula (95) Formula (2) 318 Formula (17) Formula (95) Formula (3) 319Formula (17) Formula (95) Formula (4) 320 Formula (17) Formula (95)Formula (7) 321 Formula (17) Formula (95) Formula (8) 322 Formula (17)Formula (95) Formula (13) 323 Formula (17) Formula (95) Formula (17) 324Formula (17) Formula (95) Formula (28) 325 Formula (17) Formula (95)Formula (41) 326 Formula (17) Formula (102) Formula (2) 327 Formula (17)Formula (102) Formula (3) 328 Formula (17) Formula (102) Formula (4) 329Formula (17) Formula (102) Formula (7) 330 Formula (17) Formula (102)Formula (8) 331 Formula (17) Formula (102) Formula (13) 332 Formula (17)Formula (102) Formula (17) 333 Formula (17) Formula (102) Formula (28)334 Formula (17) Formula (102) Formula (41) 335 Formula (28) Formula(86) Formula (2) 336 Formula (28) Formula (86) Formula (3) 337 Formula(28) Formula (86) Formula (4) 338 Formula (28) Formula (86) Formula (7)339 Formula (28) Formula (86) Formula (8) 340 Formula (28) Formula (86)Formula (13) 341 Formula (28) Formula (86) Formula (17) 342 Formula (28)Formula (86) Formula (28) 343 Formula (28) Formula (86) Formula (41) 344Formula (28) Formula (87) Formula (2) 345 Formula (28) Formula (87)Formula (3) 346 Formula (28) Formula (87) Formula (4) 347 Formula (28)Formula (87) Formula (7) 348 Formula (28) Formula (87) Formula (8) 349Formula (28) Formula (87) Formula (13) 350 Formula (28) Formula (87)Formula (17) 351 Formula (28) Formula (87) Formula (28) 352 Formula (28)Formula (87) Formula (41) 353 Formula (28) Formula (91) Formula (2) 354Formula (28) Formula (91) Formula (3) 355 Formula (28) Formula (91)Formula (4) 356 Formula (28) Formula (91) Formula (7) 357 Formula (28)Formula (91) Formula (8) 358 Formula (28) Formula (91) Formula (13) 359Formula (28) Formula (91) Formula (17) 360 Formula (28) Formula (91)Formula (28) 361 Formula (28) Formula (91) Formula (41) 362 Formula (28)Formula (93) Formula (2) 363 Formula (28) Formula (93) Formula (3) 364Formula (28) Formula (93) Formula (4) 365 Formula (28) Formula (93)Formula (7) 366 Formula (28) Formula (93) Formula (8) 367 Formula (28)Formula (93) Formula (13) 368 Formula (28) Formula (93) Formula (17) 369Formula (28) Formula (93) Formula (28) 370 Formula (28) Formula (93)Formula (41) 371 Formula (28) Formula (95) Formula (2) 372 Formula (28)Formula (95) Formula (3) 373 Formula (28) Formula (95) Formula (4) 374Formula (28) Formula (95) Formula (7) 375 Formula (28) Formula (95)Formula (8) 376 Formula (28) Formula (95) Formula (13) 377 Formula (28)Formula (95) Formula (17) 378 Formula (28) Formula (95) Formula (28) 379Formula (28) Formula (95) Formula (41) 380 Formula (28) Formula (102)Formula (2) 381 Formula (28) Formula (102) Formula (3) 382 Formula (28)Formula (102) Formula (4) 383 Formula (28) Formula (102) Formula (7) 384Formula (28) Formula (102) Formula (8) 385 Formula (28) Formula (102)Formula (13) 386 Formula (28) Formula (102) Formula (17) 387 Formula(28) Formula (102) Formula (28) 388 Formula (28) Formula (102) Formula(41) 389 Formula (41) Formula (86) Formula (2) 390 Formula (41) Formula(86) Formula (3) 391 Formula (41) Formula (86) Formula (4) 392 Formula(41) Formula (86) Formula (7) 393 Formula (41) Formula (86) Formula (8)394 Formula (41) Formula (86) Formula (13) 395 Formula (41) Formula (86)Formula (17) 396 Formula (41) Formula (86) Formula (28) 397 Formula (41)Formula (86) Formula (41) 398 Formula (41) Formula (87) Formula (2) 399Formula (41) Formula (87) Formula (3) 400 Formula (41) Formula (87)Formula (4) 401 Formula (41) Formula (87) Formula (7) 402 Formula (41)Formula (87) Formula (8) 403 Formula (41) Formula (87) Formula (13) 404Formula (41) Formula (87) Formula (17) 405 Formula (41) Formula (87)Formula (28) 406 Formula (41) Formula (87) Formula (41) 407 Formula (41)Formula (91) Formula (2) 408 Formula (41) Formula (91) Formula (3) 409Formula (41) Formula (91) Formula (4) 410 Formula (41) Formula (91)Formula (7) 411 Formula (41) Formula (91) Formula (8) 412 Formula (41)Formula (91) Formula (13) 413 Formula (41) Formula (91) Formula (17) 414Formula (41) Formula (91) Formula (28) 415 Formula (41) Formula (91)Formula (41) 416 Formula (41) Formula (93) Formula (2) 417 Formula (41)Formula (93) Formula (3) 418 Formula (41) Formula (93) Formula (4) 419Formula (41) Formula (93) Formula (7) 420 Formula (41) Formula (93)Formula (8) 421 Formula (41) Formula (93) Formula (13) 422 Formula (41)Formula (93) Formula (17) 423 Formula (41) Formula (93) Formula (28) 424Formula (41) Formula (93) Formula (41) 425 Formula (41) Formula (95)Formula (2) 426 Formula (41) Formula (95) Formula (3) 427 Formula (41)Formula (95) Formula (4) 428 Formula (41) Formula (95) Formula (7) 429Formula (41) Formula (95) Formula (8) 430 Formula (41) Formula (95)Formula (13) 431 Formula (41) Formula (95) Formula (17) 432 Formula (41)Formula (95) Formula (28) 433 Formula (41) Formula (95) Formula (41) 434Formula (41) Formula (102) Formula (2) 435 Formula (41) Formula (102)Formula (3) 436 Formula (41) Formula (102) Formula (4) 437 Formula (41)Formula (102) Formula (7) 438 Formula (41) Formula (102) Formula (8) 439Formula (41) Formula (102) Formula (13) 440 Formula (41) Formula (102)Formula (17) 441 Formula (41) Formula (102) Formula (28) 442 Formula(41) Formula (102) Formula (41)

Preference is furthermore given to compounds of the formula (1) in whichthe symbol p=1 or p=2. Particular preference is given to compounds wherep=1. This preference also applies to the combinations of Ar¹, Ar² andAr³ shown above in Tables 1, 2 and 3.

Preference is furthermore given to compounds of the formula (1) in whichthe symbol X is selected, identically or differently on each occurrence,from the group consisting of B(R²), C(R²)₂, Si(R²)₂, O, S or N(R²),particularly preferably C(R²)₂, S or N(R²). Very particularlypreferably, all symbols X stand, identically or differently on eachoccurrence, for C(R²)₂. R² here preferably stands for an alkyl or arylgroup.

Ar¹, Ar² and Ar³ are particularly preferably selected as shown in Tables1 and 2, and X simultaneously stands, identically or differently on eachoccurrence, for C(R²)₂. R² here preferably stands for an alkyl or arylgroup.

Particular preference is given to compounds of the formula (1) selectedfrom the formulae (111) to (141), where the aromatic systems may eachalso be substituted by one or more radicals R¹:

Preference is furthermore given to compounds of the formula (1) in whichthe symbol R¹, which may be bonded to Ar¹, Ar² or Ar³ as a substituent,is selected on each occurrence, identically or differently, from thegroup consisting of H, D, F, Si(R³)₃, straight-chain alkyl or alkoxygroups having 1 to 10 C atoms or branched or cyclic alkyl or alkoxygroups having 3 to 10 C atoms, each of which may be substituted by oneor more radicals R³, where in each case one or more non-adjacent CH₂groups may be replaced by R³C═CR³ or O and where one or more H atoms maybe replaced by F, or aromatic or heteroaromatic ring systems having 5 to40 aromatic ring atoms, or a combination of these systems; two or moresubstituents R¹ here may also form a mono- or polycyclic, aliphatic oraromatic ring system with one another. The substituent R¹ isparticularly preferably selected from H, D, straight-chain alkyl groupshaving 1 to 6 C atoms, branched or cyclic alkyl groups having 3 to 6 Catoms or an aromatic or heteroaromatic ring system having 5 to 24aromatic ring atoms; two or more substituents R¹ here may also form amono- or polycyclic ring system with one another. The substituent R¹ isvery particularly preferably selected from H, D, alkyl groups selectedfrom methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl,cyclopentyl or cyclohexyl, in particular methyl or tert-butyl, andaromatic or heteroaromatic ring systems selected from the groupconsisting of unsubstituted or R³-substituted phenyl, naphthyl,benzimidazole, which may also be substituted by phenyl,phenylbenzimidazole, where the benzimidazole may also be substituted byphenyl or other radicals R³, or triazine, which may also be substitutedby phenyl or other radicals R³.

Preference is furthermore given to compounds of the formula (1) in whichthe symbol R², which is bonded to the group X, is selected on eachoccurrence, identically or differently, from H, straight-chain alkylgroups having 1 to 10 C atoms or branched or cyclic alkyl groups having3 to 10 C atoms, where in each case one or more non-adjacent CH₂ groupsmay be replaced by —R²C═CR²— or —O— and where one or more H atoms may bereplaced by F, or a monovalent aryl or heteroaryl group having 5 to 16aromatic ring atoms, which may be substituted by one or morenon-aromatic radicals R²; two radicals R² which are bonded in the samegroup X may also form a ring system with one another. The radicals R²are particularly preferably selected from straight-chain alkyl groupshaving 1 to 4 C atoms or branched alkyl groups having 3 or 4 C atoms, inparticular methyl groups, or phenyl groups; two or more radicals R² heremay form a ring system with one another. If a plurality of radicals R²form a ring system with one another, a spiro structure is therebyformed. This may be preferred, in particular, if the radicals R² standfor phenyl groups or if two radicals R² stand for alkyl groups whichform a ring system with one another.

Examples of preferred compounds of the formula (1) are structures (1) to(246) depicted below.

The compounds according to the invention can be prepared by synthesissteps known to the person skilled in the art, such as, for example,Suzuki coupling and cyclisation reactions, as shown in Scheme 1 forcompounds of the formula (112). The synthesis can be carried outentirely analogously with other aryl groups Ar¹, Ar² and Ar³. It islikewise possible firstly to carry out the coupling with the naphthaleneand then the coupling with the pyrene.

To this end, a boronic acid derivative of the aromatic group Ar¹, inthis case pyreneboronic acid, is coupled to abromochlorobis(carboxylate) derivative of the aromatic group Ar², inthis case diethyl 2-bromo-5-chloro-terephthalate, with palladiumcatalysis, followed by coupling of a boronic acid derivative of thearomatic group Ar³, in this case 1-naphthylboronic acid. These selectivecoupling steps succeed due to different reactivity of chlorine andbromine. The carboxylate groups are converted into the correspondingalcohol by the addition reaction of an alkyl- or arylmetal compound, forexample an alkyl- or aryllithium compound or an alkyl- or aryl-Grignardcompound. This alcohol can be cyclised under acidic conditions, wherethe precise reaction conditions determine whether a five-membered ring,a six-membered ring or a mixture of five-membered ring and six-memberedring is formed. If a mixture of five-membered ring and six-membered ringis formed, this can be separated, for example by recrystallisation orchromatographic methods. This reaction is possible entirely analogouslywith other arylboronic acid derivatives and otherchlorobromo-dicarboxylic acid derivatives. It is likewise possible toemploy aryl groups that are already substituted. Furthermore, the use ofa 3-bromo-6-chlorophthalic acid ester enables the correspondingcis-linked derivatives to be synthesised. It is likewise possible to useother C—C linking reactions instead of a Suzuki coupling.

The present invention therefore furthermore relates to a process for thepreparation of the compounds according to the invention, comprising thefollowing reaction steps:

-   a) coupling of suitably substituted Ar¹, Ar² and Ar³, where suitable    substituents can be, for example, carboxylate groups; and-   b) cyclisation of the substituents for introduction of the bridges    X.

Preference is given to a process for the preparation of the compounds ofthe formula (1), comprising the following reaction steps:

-   a) coupling of a boronic acid or a boronic acid derivative of Ar¹ to    a bromochlorobis(carboxylate) derivative of Ar²;-   b) coupling of the reaction product from a) to a boronic acid or a    boronic acid derivative of Ar³;-   c) conversion of the carboxylate groups into alcohol groups; and-   d) cyclisation under acidic conditions.

The compounds according to the invention described above, in particularcompounds which are substituted by reactive leaving groups, such asbromine, iodine, or boronic acid or boronic acid ester, can also be usedas monomers for the production of corresponding conjugated, partiallyconjugated or non-conjugated polymers or oligomers or as the core ofdendrimers. The polymerisation here is preferably carried out via thehalogen functionality or the boronic acid functionality.

The invention furthermore relates to polymers, oligomers or dendrimerscomprising one or more compounds according to the invention, where oneor more radicals R¹ or R² represent bonds from a compound to the polymeror dendrimer. These polymers, oligomers or dendrimers may be conjugated,partially conjugated or non-conjugated.

The same preferences as described above apply to the polymer recurringunits according to the invention.

These compounds are homopolymerised or copolymerised with furthermonomers. Suitable and preferred monomers are selected from fluorenes(for example in accordance with EP 842208 or WO 00/22026),spirobifluorenes (for example in accordance with EP 707020, EP 894107 orWO 06/061181), para-phenylenes (for example in accordance with WO92/18552), carbazoles (for example in accordance with WO 04/070772 or WO04/113468), thiophenes (for example in accordance with EP 1028136),dihydrophenanthrenes (for example in accordance with WO 05/014689), cis-and trans-indenofluorenes (for example in accordance with WO 04/041901or WO 04/113412), ketones (for example in accordance with WO 05/040302),phenanthrenes (for example in accordance with WO 05/104264 or theunpublished application DE 102005037734.3) or also a plurality of theseunits. These polymers usually also contain further units, for exampleemitting (fluorescent or phosphorescent) units, such as, for example,vinyltriarylamines (for example in accordance with the unpublishedapplication DE 102005060473.0) or phosphorescent metal complexes (forexample in accordance with WO 06/003000), and/or charge-transport units,in particular those based on tri-arylamines

The compounds of the formula (1) according to the invention and thecorresponding polymers, oligomers or dendrimers are suitable for use inelectronic devices, in particular in organic electroluminescent devices(OLEDs, PLEDs). Depending on the structure, the compounds are employedin different functions and layers. The precise use of the compoundsdepends, in particular, on the choice of the aryl groups Ar¹, Ar² andAr³ and on the groups X.

The invention therefore furthermore relates to the use of the compoundsof the formula (1) according to the invention or the correspondingpolymers, oligomers or dendrimers in electronic devices, in particularin organic electroluminescent devices (OLEDs), organic field-effecttransistors (O-FETs), organic thin-film transistors (O-TFTs), organiclight-emitting transistors (O-LETs), organic integrated circuits(O-ICs), organic solar cells (O-SCs), organic field-quench devices(O-FQDs), light-emitting electro-chemical cells (LECs), organicphotoreceptors or organic laser diodes (O-Laser).

The invention furthermore relates to electronic devices, in particularthe electronic devices mentioned above, comprising at least one compoundof the formula (1) or a corresponding oligomer, polymer or dendrimer, inparticular organic electroluminescent devices comprising anode, cathodeand at least one emitting layer, characterised in that at least oneorganic layer, which may be an emitting layer or another layer,comprises at least one compound of the formula (1).

The preferred embodiments mentioned above apply to the use in theelectronic device.

Apart from cathode, anode and emitting layer, the organicelectroluminescent device may also comprise further layers. These areselected, for example, from in each case one or more hole-injectionlayers, hole-transport layers, hole-blocking layers, electron-transportlayers, electron-injection layers, electron-blocking layers,exciton-blocking layers, charge-generation layers and/or organic orinorganic p/n junctions. However, it should be pointed out that each ofthese layers does not necessarily have to be present, and the choice ofthe layers always depends on the compounds used and in particular alsoon whether it is a fluorescent or phosphorescent electroluminescentdevice.

The organic electroluminescent device may also comprise a plurality ofemitting layers, where at least one organic layer comprises at least onecompound of the formula (1) or a corresponding oligomer, polymer ordendrimer. These emission layers particularly preferably have in total aplurality of emission maxima between 380 nm and 750 nm; resultingoverall in white emission, i.e. various emitting compounds which areable to fluoresce or phosphoresce and emit blue and yellow, orange orred light are used in the emitting layers. Particular preference isgiven to three-layer systems, i.e. systems having three emitting layers,where at least one of these layers comprises at least one compound ofthe formula (1) or a corresponding oligomer, polymer or dendrimer andwhere the three layers exhibit blue, green and orange or red emission(for the basic structure, see, for example, WO 05/011013) and systemswhich have more than three emitting layers. Emitters which havebroad-band emission bands and thus exhibit white emission are likewisesuitable for white emission.

It is particularly preferred for the compounds of the formula (1) to beemployed in an emitting layer. In this case, they can be employed eitheras emitting material (emitting dopant) or as host material for anemitting material. The compounds of the formula (1) are particularlypreferably suitable as emitting material.

If the compound of the formula (1) is employed as emitting material inan emitting layer, it is preferably employed in combination with a hostmaterial. A host material is taken to mean the component in a systemcomprising host and dopant that is present in the higher proportion inthe system. In the case of a system comprising one host and a pluralityof dopants, the host is taken to mean the component whose proportion inthe mixture is the highest.

The proportion of the compound of the formula (1) in the mixture of theemitting layer is between 0.1 and 50.0% by vol., preferably between 0.5and 20.0% by vol., particularly preferably between 1.0 and 10.0% by vol.Correspondingly, the proportion of the host material is between 50.0 and99.9% by vol., preferably between 80.0 and 99.5% by vol., particularlypreferably between 90.0 and 99.0% by vol.

Suitable host materials for this purpose are materials from variousclasses of substance. Preferred host materials are selected from theclasses of the oligoarylenes (for example2,2′,7,7′-tetraphenylspirobifluorene in accordance with EP 676461 ordinaphthylanthracene), in particular the oligoarylenes containingcondensed aromatic groups, the oligoarylenevinylenes (for example DPVBior spiro-DPVBi in accordance with EP 676461), the polypodal metalcomplexes (for example in accordance with WO 04/081017), thehole-conducting compounds (for example in accordance with WO 04/058911),the electron-conducting compounds, in particular ketones, phosphineoxides, sulfoxides, etc. (for example in accordance with WO 05/084081and WO 05/084082), the atropisomers (for example in accordance with WO06/048268), the boronic acid derivatives (for example in accordance withWO 06/117052) or the benzanthracenes (for example in accordance with theunpublished application DE 102007024850.6). Particularly preferred hostmaterials are selected from the classes of the oligoarylenes containingnaphthalene, anthracene, benzanthracene and/or pyrene, or atropisomersof these compounds, the ketones, the phosphine oxides and thesulfoxides. Very particularly preferred host materials are selected fromthe classes of the oligoarylenes containing anthracene, benzanthraceneand/or pyrene, or atropisomers of these compounds. For the purposes ofthis invention, an oligoarylene is intended to be taken to mean acompound in which at least three aryl or arylene groups are bonded toone another.

Preferred host materials are, in particular, selected from compounds ofthe formula (138)Ar⁴—(Ar⁵)_(p)—Ar⁶  formula (138)where Ar⁴, Ar⁵, Ar⁶ are on each occurrence, identically or differently,an aryl or heteroaryl group having 5 to 30 aromatic ring atoms, whichmay be substituted by one or more radicals R¹, and R¹ and p have thesame meaning as described above; the sum of the π electrons in Ar⁴, Ar⁵and Ar⁶ is at least 30 if p=1 and is at least 36 if p=2 and is at least42 if p=³.

The group Ar⁵ in the host materials of the formula (138) particularlypreferably stands for anthracene, which may be substituted by one ormore radicals R¹, and the groups Ar⁴ and Ar⁶ are bonded in the 9- and10-position. Very particularly preferably, at least one of the groupsAr⁴ and/or Ar⁶ is a condensed aryl group selected from 1- and2-naphthyl, 2-, 3- and 9-phenanthrenyl and 2-, 3-, 4-, 5-, 6- and7-benzanthracenyl, each of which may be substituted by one or moreradicals R¹.

It is furthermore preferred for the compound of the formula (1) to beemployed as host material, in particular for a fluorescent dopant.

Suitable fluorescent emitters are selected, example, from the class ofthe monostyrylamines, distyrylamines, tristyrylamines,tetrastyrylamines, styrylphosphines, styryl ethers and arylamines. Amonostyrylamine is taken to mean a compound which contains one styrylgroup and at least one amine, which is preferably aromatic. Adistyrylamine is taken to mean a compound which contains two styrylgroups and at least one amine, which is preferably aromatic. Atristyrylamine is taken to mean a compound which contains three styrylgroups and at least one amine, which is preferably aromatic. Atetrastyrylamine is taken to mean a compound which contains four styrylgroups and at least one amine, which is preferably aromatic. The styrylgroups are particularly preferably stilbenes, which may also be furthersubstituted. Corresponding phosphines and ethers are defined analogouslyto the amines. For the purposes of this invention, an arylamine or anaromatic amine is taken to mean a compound which contains threesubstituted or unsubstituted aromatic or heteroaromatic ring systemsbonded directly to the nitrogen. Preferred examples thereof are aromaticanthracenamines, aromatic pyrenamines, aromatic pyrenediamines, aromaticchrysenamines or aromatic chrysenediamines. An aromatic anthracenamineis taken to mean a compound in which one diarylamino group is bondeddirectly to an anthracene group, preferably in the 9-position or in the2-position. Aromatic pyrenamines, pyrenediamines, chrysenamines andchrysenediamines are defined analogously thereto, where the diarylaminogroups are preferably bonded to the pyrene in the 1-position or in the1,6-position. Further preferred dopants are selected fromindenofluorenamines or indenofluorenediamines, for example in accordancewith WO 06/122630, benzoindenofluorenamines or benzoindenofluorenedamines, for example in accordance with WO 08/006449, anddibenzoindenofluorenamines or dibenzoindenofluorenediamines, for examplein accordance with WO 07/140847. Examples of dopants from the class ofthe styrylamines are substituted or unsubstituted tristilbenamines orthe dopants described in WO 06/000388, WO 06/058737, WO 06/000389, WO07/065549 and WO 07/115610.

Depending on the substitution pattern, the compounds of the formula (1)can also be employed in other layers.

A possible further use of compounds of the formula (1) is the use ashole-transport or hole-injection material in a hole-transport orhole-injection layer. This use is particularly suitable if one or morebridges X stand for S or NR².

A further possible use of compounds of the formula (1) is the use aselectron-transport material in an electron-transport layer. Particularlysuitable for this purpose are compounds of the formula (1) which aresubstituted by at least one electron-deficient heteroaromatic group.Electron-deficient heteroaromatic groups are 6-membered heteroaromaticgroups having at least one nitrogen atom and corresponding condensedsystems, for example pyridine, pyrazine, pyrimidine, pyridazine,triazine, quinoline, quinoxaline or phenanthroline, or 5-memberedheteroaromatic groups having at least one nitrogen atom and a furtherheteroatom selected from N, O and S, and corresponding condensedsystems, for example pyrazole, imidazole, oxazole, oxadiazole orbenzimidazole. A suitable electron-transport material is furthermorecompounds in which Ar¹, Ar² and/or Ar³ stand for an electron-deficientheterocycle. If the compounds of the formula (1) are used aselectron-transport material, the bridge X preferably stands for C(R²)₂.In addition, the compounds are also suitable as electron-transportmaterials if at least one bridge X, preferably both bridges X, stand forC═O, P(═O)R², SO or SO₂.

Preference is furthermore given to an organic electroluminescent device,characterised in that one or more layers are coated by a sublimationprocess. In this, the materials are vapour-deposited in vacuumsublimation units at an initial pressure below 10⁻⁵ mbar, preferablybelow 10⁻⁶ mbar. However, it is also possible for the initial pressureto be even lower, for example below 10⁻⁷ mbar.

Preference is likewise given to an organic electroluminescent device,characterised in that one or more layers are coated by the OVPD (organicvapour phase deposition) process or with the aid of carrier-gassublimation. Here, the materials are applied at a pressure between 10⁻⁵mbar and 1 bar. A special case of this process is the OVJP (organicvapour jet printing) process, in which the materials are applieddirectly through a nozzle and are thus structured (for example M. S.Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

Preference is furthermore given to an organic electroluminescent device,characterised in that one or more layers are produced from solution,such as, for example, by spin coating, or by means of any desiredprinting process, such as, for example, screen printing, flexographicprinting or offset printing, but particularly preferably LITI(light-induced thermal imaging, thermal transfer printing) or ink-jetprinting. Soluble compounds of the formula (1) are necessary for thispurpose. High solubility can be achieved by suitable substitution of thecompounds. A coating method from solution is also particularly suitablefor oligomers, polymers or dendrimers.

For application from solution, solutions of the compounds according tothe invention in one or more solvents are necessary. The inventiontherefore furthermore relates to solutions of the compounds according tothe invention or corresponding oligomers, polymers or dendrimers in oneor more solvents. The solution here may also comprise furtherconstituents, for example a host material for the compound according tothe invention.

On use in organic electroluminescent devices, the compounds according tothe invention have the following surprising advantages over the priorart:

-   1. The compounds according to the invention exhibit dark-blue    emission on use as emitting materials in organic electroluminescent    devices (CIE y in the range from 0.10 to 0.13) and are thus    eminently suitable for the production of dark-blue-emitting    electroluminescent devices.-   2. A suitable choice of the groups Ar¹, Ar² and Ar³ enables the    colour location of the emission from the compound to be set simply    using the compounds according to the invention. Thus, both    deep-blue- and also pale-blue-emitting compounds are accessible,    where the colour location can in each case be optimised for the    desired use.-   3. The electroluminescent devices furthermore exhibit very good    efficiencies (EQE>6%).-   4. Furthermore, electroluminescent devices comprising the compounds    according to the invention exhibit a significant improvement with    respect to the lifetime.-   5. In particular on use in the electron-injection and -transport    layer of doped electron-transport materials which result in an    excess of electrons in the device, the compounds according to the    invention, if employed as emitters, exhibit significant improvements    with respect to efficiency and lifetime compared with emitters in    accordance with the prior art which contain diarylamino groups. This    is an essential advantage since the very combination of LiQ with    benzimidazole derivatives is frequently used as electron-transport    material.

The invention is described in greater detail by the following examples,without wishing to restrict it thereby. The person are skilled in theart will be able, without being inventive, to carry out the inventionthroughout the range disclosed and thus produce further materials andorganic electroluminescent devices according to the invention.

EXAMPLES

The following syntheses were carried out under a protective-gasatmosphere, unless indicated otherwise. The starting materials werepurchased from ALDRICH or ABCR.

Example 1: Synthesis of1,1-dimethylbenzindeno-1,1-dimethylindeno-[a]pyrene a) Diethyl2-chloro-5-pyren-1-ylterephthalate

28.9 g (103 mmol) of bromopyrene are dissolved in 275 ml of dry THF, thesolution is cooled to −75° C., and 52 ml (104 mmol) of a 2 M solution ofn-butyllithium are added dropwise at this temperature. The yellowsuspension is stirred at −75° C. for 1 h, and 17.5 ml (155 mmol) oftrimethyl borate are then added dropwise. After the mixture has beenwarmed to RT, 34.5 g (103 mmol) of diethyl chlorobromoterephthalate, 22g (206 mmol) of Na₂CO₃, 1.2 g (1.03 mmol) oftetrakis(triphenylphosphine)palladium(0), 140 ml of H₂O, 280 nil oftoluene and 140 ml of EtOH are added, and the mixture is heated at theboil for 2 h. After the organic phase has been separated off, washedtwice with water and dried over Na₂SO₄, the solvent is removed in vacuo,and the oil which remains is brought to crystallisation in heptane.Recrystallisation twice gives the product in the form of a colourlesssolid (33 g, 70%) and a purity of >98%, which is employed in this formin the subsequent reaction.

b) Diethyl 2-naphthalen-1-yl-5-pyren-1-ylterephthalate

43.5 g (90 mmol) of diethyl 2-chloro-5-pyren-1-ylterephthalate, 21.5 g(120 mmol) of 1-naphthylboronic acid and 58.1 g of Cs₂CO₃ are initiallyintroduced in 230 nil of dry dioxane, and the mixture is saturated withN₂ for 30 min. 2.7 ml of a 1.0 M solution of tri-tert-butylphosphine intoluene, followed by 300 mg (1.3 mmol) of Pd(OAc)₂, are then added. Themixture is heated at the boil for 4 h and extended with water and EtOH,and the precipitate is filtered off with suction, washed with water andEtOH and dried. The solid is recrystallised three times from dioxane andthen has a purity of >99% according to ¹H-NMR. The yield is 44.2 g (90%)of colourless solid.

The following compounds (Examples 2b to 10b) are prepared analogously tothe process described above.

Ex. Structure Yield (%) 2b

95 3b

50 4b

53 5b

67 6b

12 7b

36 8b

50 9b

62 10b 

75

c)2-[4-(1-Hydroxy-1-methylethyl)-2-naphthalen-1-yl-5-pyren-1-ylphenyl]propan-2-ol

30 g (55 mol) of diethyl 2-naphthalen-1-yl-5-pyren-1-ylterephthalate aredissolved in 270 ml of dry THF, 110 ml (330 mmol) of a 3 Mmethylmagnesium chloride solution in THF are added dropwise at 5° C.,and the mixture is stirred at RT for 12 h. After the reaction has beeninterrupted by addition of 180 ml of 25% acetic acid, the mixture isworked up by extraction with ethyl acetate/water, dried over Na₂SO₄ andevaporated in a rotary evaporator. Recrystallisation from EtOH/tolueneleaves 26.3 g (92%) of colourless solid, which has a purity of >98%according to ¹H-NMR.

The following compounds (Examples 2c to 9c) are prepared analogously tothe process described above. In Example 10c, phenyllithium is employedas reagent instead of methylmagnesium chloride.

Ex. Structure Yield (%) 2c

92 3c

78 4c

94 5c

80 6c

73 7c

90 8c

quant. 9c

quant. 10c 

quant.

d) 1,1-Dimethylbenzindeno-1,1-dimethylindeno[a]pyrene

26.3 g (50.5 mmol) of2-[4-(1-hydroxy-1-methylethyl)-2-naphthalen-1-yl-5-pyren-1-ylphenyl]propan-2-olare dissolved in 750 ml of dichloromethane, 45 ml of methanesulfonicacid in 70 g of polyphosphoric acid are added dropwise at −20° C., andthe mixture is stirred at this temperature for 1 h. When the reaction iscomplete, 400 ml of EtOH are added dropwise, the mixture is heated atthe boil for 1 h, and the yellow solid is filtered off.Recrystallisation four times from NMP and sublimation twice in vacuo(p=1×10⁻⁵ mbar, T=340° C.) gives a yellow powder having a purity>99.9%(16 g, 65%).

The following compounds (Examples 2d to 10d) are prepared analogously tothe process described above.

Ex. Structure Yield (%) 2d

27 3d

41 4d

50 5d

15 6d

32 7d

10 8d

53 9d

37 10d 

37

Example 11: Synthesis of1,1-dimethylbenzindeno-1,1-dimethylindeno[b]fluoranthene a) Diethyl2-chloro-5-naphthalen-1-ylterephthalate

51 g (298 mmol) of 1-naphthylboronic acid, 100 g (298 mmol) of diethylchlorobromoterephthalate and 144 g (626 mmol) of potassium phosphatemonohydrate are initially introduced in a mixture of 600 ml of dist.water, 400 ml of toluene and 200 ml of dioxane and saturated with N₂ for30 min. 5.4 g (18 mmol) of tri(o-tolyl)phosphine and 669 mg (3 mmol) ofpalladium(II) acetate are subsequently added, and the mixture is heatedat the boil for 3 h. After dilution with toluene, the organic phase isseparated off, washed twice with water, dried over Na₂SO₄ and evaporatedin vacuo. The oil which remains is distilled in a thin-film evaporator(p=5×10⁻³ mbar, T=130° C.) and isolated in the form of a yellow oil (74g, 65%), which, according to ¹H-NMR, has a purity of >95%.

b) Diethyl 2-fluoranthen-3-yl-5-naphthalen-1-ylterephthalate

15.4 g (40 mmol) of diethyl 2-chloro-5-naphthalen-1-ylterephthalate,14.0 g (56 mmol) of fluoranthene-3-boronic acid and 17.7 g of Cs₂CO₃ areinitially introduced in 70 ml of dry dioxane and saturated with N₂ for30 min. 0.8 ml of a 1.0 M solution of tri-tert-butylphosphine intoluene, followed by 91 mg (0.4 mmol) of Pd(OAc)₂ are then added. Themixture is heated at the boil for 4 h, extended with water and EtOH, theprecipitate is filtered off with suction, washed with heptane and dried.The solid is recrystallised from toluene and then has, according to¹H-NMR, a purity of >95%. The yield is 8.5 g (38%) of colourless solid.

c)2-[4-(1-Hydroxy-1-methylethyl)-2-fluoranthen-3-yl-5-naphthalin-1-ylphenyl]propan-2-ol

8.5 g (15 mol) of diethyl2-fluoranthen-3-yl-5-naphthalin-1-ylterephthalate are dissolved in 75 mlof dry THF, 31 ml (93 mmol) of a 3 M methylmagnesium chloride solutionin THF are added at 5° C., and the mixture is stirred at RT for 12 h.After interruption of the reaction by addition of 30 ml of 25% aceticacid, the mixture is worked up by extraction with ethyl acetate/water,dried over Na₂SO₄ and evaporated in a rotary evaporator, giving 8.0 g(99%) of the crude product, which is employed in the next step withoutfurther purification.

d) 1,1-Dimethylbenzindeno-1,1-dimethylindeno[b]fluoranthene

8.0 g (15.4 mmol) of2-[4-(1-hydroxy-1-methylethyl)-2-fluoranthen-3-yl-5-naphthalen-1-ylphenyl]propan-2-olare dissolved in 250 ml of dichloromethane, 15 ml of methanesulfonicacid in 22 g of polyphosphoric acid are added dropwise at −20° C., andthe mixture is stirred at this temperature for 1 h. When the reaction iscomplete, 130 ml of EtOH are added dropwise, the mixture is heated atthe boil for 1 h, and the yellow solid is filtered off.Recrystallisation twice from toluene and sublimation twice in vacuo(p=4×10⁻⁶ mbar, T=300° C.) gives a yellow powder having a purityof >99.9% (1.9 g, 25%).

Example 12: Synthesis of1,1-diphenylbenzindeno-1,1-diphenyl-indeno[a]pyrene

The synthesis is carried out analogously to Example 1, withphenylmagnesium chloride solution being used instead of methylmagnesiumchloride solution in step c).

Example 13: Production of OLEDs

OLEDs are produced by a process which is described in general in WO04/058911 and which is adapted in individual cases to the particularcircumstances (for example layer-thickness variation in order to achieveoptimum efficiency or colour).

The results for various OLEDs are presented in Examples 14 to 31 below.Glass plates which have been coated with structured ITO (indium tinoxide) form the substrates of the OLEDs. The OLEDs consist of thefollowing layer sequence: substrate/hole-injection layer(HIM)/hole-transport layer (HTM1) 60 nm/hole-transport layer (HTM2) 20nm/emission layer (EML) 30 nm/electron-transport layer (ETM) 20 nm andfinally a cathode. The materials are thermally vapour-deposited in avacuum chamber. The emission layer here always consists of a matrixmaterial (host) and a dopant, which is admixed with the host byco-evaporation. The cathode is formed by a 1 nm thin LiF layer and a 100nm Al layer deposited on top. Table 4 shows the chemical structures ofthe materials used to build up the OLEDs.

These OLEDs are characterised by standard methods; for this purpose, theelectroluminescence spectra, the efficiency (measured in cd/A), thepower efficiency (measured in lm/W) as a function of the luminance,calculated from current-voltage-luminance characteristic lines (IULcharacteristic lines), and the lifetime are determined. The lifetime isdefined as the time after which the initial luminance of 6000 cd/m² (forblue-emitting OLEDs) or 25,000 cd/m² (for green-emitting OLEDs) hasdropped to half.

Tables 5 and 6 show the results for some OLEDs (Examples 14 to 31). Thehost materials and emitter materials according to the invention are thecompounds of Examples 1d, 2d, 5d and 12. The comparative examples usedare host H1 and emitters D1, D2 or D3 in accordance with the prior art.

As is clearly evident from the results in Tables 5 and 6, organicelectroluminescent devices comprising the compounds according to theinvention have a significantly longer lifetime for use of the compoundaccording to the invention as matrix material and improved colourcoordinates and a significantly longer lifetime for use as dopantscompared with materials in accordance with the prior art.

TABLE 4

HTM1

HTM 2

HIM

ETM1

ETM 2

ETM3

H2

H1

D1

D2

D3

Bsp. 1d

Ex. 12

Ex. 2d

Ex. 5d

TABLE 5 Life- Eff. time (cd/A) Voltage at at (V) at 25000 1000 1000cd/m² Ex. EML ETM Colour cd/m² cd/m² CIE (h) 14 H1 + ETM2 green 16.3 5.2x = 300 (comp.) 9% of 0.29/ y = D1 0.60 15 Ex. 12 + ETM2 green 18.1 4.3x = 320 0.29/ 9% y = of D1 0.61

TABLE 6 Volt- Life- time Max. age at effi- (V) at 6000 Exam- ciency 1000cd/m² ple EML ETM Colour (cd/A) cd/m² CIE (h) 16 H1 + ETM1 blue 4.1 5.3x = 160 (comp.) 5% 0.14/ of D2 y = 0.16 17 H2 + ETM1 blue 4.3 5.2 x =180 (comp.) 5% 0.14/ of D2 y = 0.15 18 H2 + ETM1 blue 1.5 5.1 x = 30(comp.) 5% 0.16/ of D3 y = 0.10 19 H1 + H2 (50%) + blue 4.9 5.0 x = 90(comp.) 5% ETM3 0.14/ of D2 (50%) y = 0.16 20 H2 + H2 (50%) + blue 5.34.9 x = 120 (comp.) 5% ETM3 0.14/ of D2 (50%) y = 0.15 21 H2 + H2(50%) + blue 1.9 5.0 x = 65 (comp.) 5% ETM3 0.16/ of D3 (50%) y = 0.0922 H2 + ETM1 blue 3.5 5.9 x = 230 5% of 0.15/ Ex. 1d y = 0.14 23 H2 +ETM2 blue 3.0 5.8 x = 210 3% of 0.15/ Ex. 1d y = 0.11 24 H2 + H2 (50%) +blue 6.4 4.6 x = 240 5% of ETM3 0.15/ Ex. 1d (50%) y = 0.13 25 H2 + H2(50%) + blue 5.5 4.4 x = 260 1% of ETM3 0.14/ Ex. 1d (50%) y = 0.11 26H2 + H2 (50%) + blue 4.7 4.8 x = 260 1% of ETM3 0.15/ Ex. 2d (50%) y =0.10 27 H2 + H2 (50%) + blue 5.0 4.7 x = 270 5% of ETM3 0.15/ Ex. 2d(50%) y = 0.11 28 H2 + ETM2 blue 4.6 5,4 x = 290 5% of 0.15/ Ex. 2d y =0.11 29 H2+ H2 (50%) + blue 7.4 4.7 x = 300 1% of ETM3 0.14/ Ex. 5d(50%) y = 0.15 30 H2 + H2 (50%) + blue 7.8 4.5 x = 310 5% of ETM3 0.14/Ex. 5d (50%) y = 0.16 31 H2 + ETM2 blue 6.8 5.3 x = 330 5% of 0.14/ Ex.5d y = 0.16

The invention claimed is:
 1. An electroluminescent element comprising acompound of formula (111) to (128), (138) or (139)

wherein where the aromatic systems may each also be substituted by oneor more radicals R¹; R¹ and R² are on each occurrence, identically ordifferently, H, D, F, Cl, Br, I, C(═O)Ar⁴, P(═O)(Ar⁴)₂, S(═O)Ar⁴,S(═O)₂Ar⁴, CR²═CR²Ar⁴, CHO, CR³═C(R³)₂, CN, NO₂, Si(R³)₃, B(OR³)₂,B(R³)₂, B(N(R³)₂)₂, OSO₂R³, a straight-chain alkyl, alkoxy or thioalkoxygroup having 1 to 40 C atoms or a straight-chain alkenyl or alkynylgroup having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl,alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each ofwhich are optionally substituted by one or more radicals R³, where ineach case one or more non-adjacent CH₂ groups are optionally replaced byR³C═CR³, C≡C, Si(R³)₂, Ge(R³)₂, Sn(R³)₂, C═O, C═S, C═Se, C═NR³, P(═O)R³,SO, SO₂, O, S or CONR³ and where one or more H atoms are optionallyreplaced by F, Cl, Br, I, CN or NO₂, or an aromatic or heteroaromaticring system having 5 to 60 aromatic ring atoms, which in each case areoptionally substituted by one or more radicals R³, or a combination ofthese systems; and wherein two or more substituents R¹ or R² optionallydefine a mono- or polycyclic, aliphatic or aromatic ring system with oneanother; Ar⁴ is on each occurrence, identically or differently, anaromatic or heteroaromatic ring system having 5-30 aromatic ring atoms,which are optionally substituted by one or more non-aromatic radicalsR¹; and wherein two radicals Ar on the same nitrogen or phosphorus atomare optionally linked to one another here by a single bond or a bridgeX; R³ is on each occurrence, identically or differently, H or analiphatic or aromatic hydrocarbon radical having 1 to 20 C atoms; as ablue emitting compound in the emitting layer, where the compound offormula is present in the emitting layer in combination with a hostmaterial selected from the group consisting of oligoarylenes,oligoarylenes containing condensed aromatic groups, anthracenes,oligoarylenevinylenes, polypodal metal complexes, hole-conductingcompounds, electron-conducting compounds, ketones, phosphine oxides,sulfoxides, boronic acid derivatives, benzanthracenes, and where thecompound of formula is present in the emitting layer in a proportion of0.5 to 20% by vol.
 2. The electroluminescent element according to claim1 wherein R¹ is selected on each occurrence, identically or differently,from H, D, F, Si(R³)₃, straight-chain alkyl or alkoxy groups having 1 to10 C atoms or branched or cyclic alkyl or alkoxy groups having 3 to 10 Catoms, each of which are optionally substituted by one or more radicalsR³, where in each case one or more non-adjacent CH₂ groups may bereplaced by R³C═CR³ or O and where one or more H atoms are optionallyreplaced by F, or aromatic or heteroaromatic ring systems having 5 to 40aromatic ring atoms, or a combination of these systems; and wherein twoor more substituents R¹ optionally define a mono- or polycyclic,aliphatic or aromatic ring system with one another.
 3. Theelectroluminescent element according to claim 1, wherein R² is selectedon each occurrence, identically or differently, from H, straight-chainalkyl groups having 1 to 10 C atoms or branched or cyclic alkyl groupshaving 3 to 10 C atoms, where in each case one or more non-adjacent CH₂groups are optionally replaced by —R²C═CR²— or —O— and where one or moreH atoms are optionally replaced by F, or a monovalent aryl or heteroarylgroup having 5 to 16 aromatic ring atoms, which may be substituted byone or more non-aromatic radicals R²; and wherein two radicals R² whichare bonded in the same group X optionally form a ring system with oneanother.
 4. The electroluminescent element according to claim 1, whereinthe host material is selected from anthracenes.